CN1137976C - Modified aluminosilicate - Google Patents
Modified aluminosilicate Download PDFInfo
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- CN1137976C CN1137976C CNB971930600A CN97193060A CN1137976C CN 1137976 C CN1137976 C CN 1137976C CN B971930600 A CNB971930600 A CN B971930600A CN 97193060 A CN97193060 A CN 97193060A CN 1137976 C CN1137976 C CN 1137976C
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/026—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/12—Water-insoluble compounds
- C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
- C11D3/1246—Silicates, e.g. diatomaceous earth
- C11D3/128—Aluminium silicates, e.g. zeolites
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- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
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- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Detergent Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A modified aluminosilicate in powder form comprising alkali metal silicate deposited onto aluninosilicate of the zeolite P type particles presents increased liquid carrying capacity.
Description
Invention field
The present invention relates to a kind of modified aluminosilicate, more ad hoc relate to a kind of modified aluminosilicate in detergent composition P type zeolite commonly used.
Background of invention
Use P type zeolite in the detergent formulation, for example in European patent Shen 0384070 (Unilever company), be identified.
P type zeolite comprises a series of synthetic zeolite facies, and these zeolite facies can (also claim Type B or P for cube configuration
cType) or cubic configuration (also claim P
1But be not limited to these types type).The structure of P type zeolite and characteristic are described in the works of Donald W.Breck " zeolite molecular sieve (Zeolite MolecularSieves) " (1974 and 1984 are published by Robert E.Krieger of Florida USA) to some extent.The typical divided oxide minor of P type molecular sieve:
M
2/nO·Al
2O
3·1.80～5.00 SiO
2·5H
2O
M is a n valency positively charged ion, and it is a kind of basic metal in the present invention, and promptly lithium, sodium, potassium, caesium or rubidium serve as preferred with sodium and potassium, and sodium is positively charged ion commonly used in the Industrial processes.
Therefore, sodium exists as main positively charged ion, and having a small amount of another kind of basic metal again can provide special benefit.
Now, used zeolite in the detergent composition except that numerous characteristics such as calcium binding capacity, the effective binding capacity of calcium and calcium absorption speed, also must present and can make them be used as other performance of the buider of dense detergent composition.
Be used for ability and its carrier fluid amount of the buider of this dense prescription, be also referred to as oily receptivity, directly related.Its carrier fluid amount is high more, and detergent composition can be dense more.
In addition, a kind of new non-drying process with atomizing manufacturing process that is called proposes, and powder detergent composition was produced by drying process with atomizing in the past.The carrier fluid amount of buider seems even more important in these methods.
Known now, the carrier fluid amount of some product is relevant with drying conditions, can change in a bigger scope.For example, disclosed zeolite P in EP-B-0384070, its carrier fluid amount is relevant with drying conditions, can reach 50～65% to 100～110% scope, and the numerical value that is reached under industrially drying such as spraying drying, turbine drying, flash drying or hurried～cyclic drying condition is lower.
Therefore, even the carrier fluid amount of disclosed zeolite P can make it be used as buider in the dense detergent composition among the EP-B-0384070, but under the industrially drying condition, still need further to improve its carrier fluid amount.
On the other hand, although add silicate for preventing corrosion in detergent composition, promote detergent bleach stability and play anti-redeposition effect aspect all particularly useful, its application in detergent composition obviously reduces for various reasons.
At first, most detergent composition still use zeolite A (such as can be from Crosfield Ltd., the Doucil P that company obtains) as buider.Now, as you know, when zeolite A and silicate are dry together, can form the megalump insolubles and remain on the fabric.
The second, because security reason SiO
2: Na
2The O mol ratio is among 1.6～3.2 water glass is being eliminated, and this is because it is alkalescence and has been belonged to pungency and so on.Though silicate mol ratio 〉=3.3 safety be difficult for dissolving, and the silicate of mol ratio＜1.6 is corrosive.Therefore needing a kind of new approach makes basic metal introduce unlikely the problems referred to above that occur in the detergent composition.
Have been found that a kind of particular combinations of the silico-aluminate and an alkali metal salt of P type zeolite now, it can increase the carrier fluid amount of zeolite on the one hand greatly, can make product no longer include pungency and residue do not occur on fabric on the other hand again.
Test and definition
I), weight-mean diameter, d
50:
d
50The expression diameter occupies the diameter of all particle weight 50% less than the particle of certain numerical value, and this parameter can be measured with the commercially available Micromeritics instrument of a kind of SesigrapH-5100 type (trade mark).
Ii), pH value
Preparation 5% (by dried solid) zeolite～softening water dispersion system uses Orion 9173 b pH electrode to measure the pH value of system on Orion EA 940 ion analysers.
Iii), CEBC (the effective binding capacity of calcium):
Measure CEBC having under the supporting electrolyte situation, the actual index that calcium ion absorbs in the washing soln environment is provided.Each zeolite sample elder generation balance above saturated nacl aqueous solution is measured the water yield again to constant weight.Each counter-balanced sample is pressed in an amount equivalent to 1gdm
-3(dried solid) is dispersed in water (1cm
3) in, again the dispersion system (1cm of gained
3) be injected into and after stirring, contain 0.01MNaCl (50ml) and 0.05M CaCl
2In the solution (3.923ml), make the solution that cumulative volume is 54.923ml thus.This is equivalent to the concentration of every liter of 200mg CaO, that is is 1.00 the absorbable theoretical maximum of zeolite (197mg) just greater than the ratio of Si: Al.Use Ca
++Ion selective electrode is measured Ca
++Ionic concn changes, and gets final reading after 15 minutes.Temperature is constant in all the time 25 ℃.From initial concentration, deduct the Ca that is measured
++Concentration promptly obtains effective calcium binding capacity CaOmg/g zeolite (in butt) of zeolite sample.
Iv) LCC (carrier fluid amount)
This measures on ASTM spatula polishing (American of Test Material StandardsD281) basis, the ultimate principle of test is, with a spatula on smooth surface to nonionic (Synperonic A3, obtain by ICI company) and granular zeolite carry out ground and mixed, cut not broken or cut continuous paste putty up to forming with spatula.Then the weight substitution equation of used nonionic thing:
=gram nonionic thing/100 gram zeolites
V) sand content (grit)
Sand content is defined as the particulate percentage ratio that is retained on the 45 μ m sieves herein.With zeolite water furnishing pulpous state, ultrasonication 15 minutes is put to sifting machine (Mocker) again in beaker.Then water (hydraulic pressure 4Bar) washes sifting machine for some time.
Take off screen cloth from machine, dry in baking oven (90 ℃ 15 minutes) measure the residue amount again.
Summary of the invention
Primary and foremost purpose of the present invention provides the powdered modified silico-aluminate that has deposited alkalimetal silicate on a kind of silico-aluminate of the P of being included in zeolite granular.
Preferably, the silicon/aluminum ratio of the silico-aluminate of P type zeolite is not more than 1.33, preferably is not more than 1.07.Also preferably, its effective calcium binding capacity is at least 140 milligrams of CaO/ gram zeolites (by butt).
Because alkalimetal silicate has been deposited on the silico-aluminate, just obtained the complete uniform mixture of these two kinds of products, this means that two kinds of products are equally distributed when being introduced into detergent composition, silico-aluminate in detergent composition/alkalimetal silicate weight ratio does not have local variation.
PH value according to modified aluminosilicate of the present invention is 10～12.Thisly make the product nonirritant than low alkalinity.And the weight ratio uniform distribution of alkalimetal silicate and silico-aluminate means especially also and does not exist the pH value that occurs owing to silico-aluminate/alkalimetal silicate local variation to change that this makes by silico-aluminate of modification of the present invention safe especially.
Be typically, contain 0～25% water, preferably be not more than 12% (weight) according to the powdery silico-aluminate of modification of the present invention.
Preferably, this modified aluminosilicate comprises the silico-aluminate (by butt) of 65～90%P type zeolite, is preferably 70～87%, most preferably be 75～85%, and 1～20% alkalimetal silicate (by butt), be preferably 3～15%, most preferably be 5～10%.More preferably be that this (P type zeolite aluminosilicate/alkalimetal silicate) weight ratio is 100/20～100/1, be preferably 100/15～100/3, more preferably 100/10～100/5.
It is further preferred that alkalimetal silicate is a water glass, its SiO
2: Na
2The O mol ratio is between 1.6～4.
It is further preferred that by the silico-aluminate of modification of the present invention, its weight in average granularity is 1～10 μ m, is preferably 1.5～6 μ m, more preferably 2.5～5 μ m.Such size-grade distribution helps avoid and form residue on fabric.
Silico-aluminate by modification of the present invention has the good washing characteristic, and CEBC is generally 110～160 milligrams of CaO/ gram modified aluminosilicates (by butt), more preferably 130～155 milligrams of CaO/ gram modified aluminosilicates (by butt).
In modified aluminosilicate of the present invention, can add various other additives, the additive that is selected from phosphonate, aminocarboxylate, multi-carboxylate, Citrate trianion and composition thereof that also can further comprise significant quantity, addition is 0.3～5.0% (by a butt) of described modified aluminosilicate usually.
Also can further make it granulating by modified aluminosilicate of the present invention by standard granulation/coalescent method.
Second purpose of the present invention is to provide a kind of method of producing modified aluminosilicate, wherein alkalimetal silicate joined to contain solid 20～46%, and more preferably in 30～40% the P type zeolite aluminosilicate slurry, further drier gained mixture.
Preferably, alkalimetal silicate is a water glass, SiO
2: Na
2The O mol ratio is between 1.6～4.
Also preferably, alkalimetal silicate adds with solution state, but also can be Powdered.
Alkalimetal silicate preferably joins in the not dry P type zeolite slurry as embodiment 11 gained of EP-A-565 364 patents.The P type zeolite of undried refers to washing and filters the back but undried P type zeolite.
Notice that now when the filter cake that rapid drying obtains by the open method of EP-A-565364, the median size of P type zeolite is decreased to about 1 μ m from about 3 μ m.Now, if before dry the water glass of adding at least 3～4%, average size of products can remain unchanged.This behavior has caused wonderful result, and for greater particle size, the carrier fluid amount of final product (modified aluminosilicate of the present invention) has but increased, and all prior arts are all thought, the carrier fluid amount just can increase when particle diameter reduces.
Grind this material, can descend by the carrier fluid amount of modified aluminosilicate of the present invention.
Preferably, introduce carbonic acid gas between dry epoch.Do like this part alkalimetal silicate is neutralized.
Can be added in the detergent composition of various physical aspects such as powder, liquid, gel and solid piece bar by washing buider consumption commonly used by modified aluminosilicate of the present invention.
Modified aluminosilicate material of the present invention can be used alone as the washing buider, or can use with other washing buider material such as zeolite A or zeolite P.Except that the crystalline silico-aluminate buider of having mentioned, also can there be other inorganic or organic buider to exist.The inorganic buider that can exist comprises yellow soda ash, amorphous aluminosilicate and phosphoric acid salt (buider), for example, and sodium orthophosphate, trisodium phosphate and tripoly phosphate sodium STPP.
Washing buider total amount optimum range is 20～80% (weights) in this composition, and this can be made up of modified aluminosilicate material of the present invention whole or in part.The alumino-silicate materials of modification of the present invention if desired, can be used in combination with other silico-aluminate such as A type zeolite.The total amount of alumino-silicate materials for example can be preferably the scope of 10～60% (weights) in the scope of 5～80% (weights) in this constituent.
Organic buider that can add in addition comprises the multipolymer of polycarboxylate polymkeric substance such as polyacrylic ester and acrylic acid or the like/Malaysia acids, polycarboxylate monomer such as citrate, gluconate, oxidation disuccinate, single, two, three succsinic acid glyceryl ester, the carboxymethyl succinate oxidation ester, carboxymethyl oxidation malonic ester, two picoline acid esters, hydroxyethyl diglycinee ester, alkyl and thiazolinyl malonic ester and succinate, and alpha-sulfonated fatty hydrochlorate.
Particularly preferred organic buider is a citrate, and dosage is 5～30% (weights), is preferably 10～25% (weights), and acrylic polymers, acrylic acid or the like/toxilic acid analog copolymer more particularly, dosage is 0.5～15% (weight), is preferably 1～10% (weight).
No matter buider is inorganic or organically, is preferably an alkali metal salt, especially sodium-salt type.
The silico-aluminate of modification of the present invention is specially adapted to not contain or contains the inorganic phosphate buider less, as the detergent composition of tripoly phosphate sodium STPP, sodium orthophosphate and trisodium phosphate.
The detergent composition that contains modified aluminosilicate of the present invention also can comprise a kind of or several detergent-active compounds as main component, they can be selected from negatively charged ion, positively charged ion, nonionic, both sexes (soda acid) and both sexes (negative and positive) the ionic activity compound of soap class and on-soap, and composition thereof.Many suitable detergent-active compounds all are that market is available, for example among " Surface-Active Agent and Detergent " (Volume I and II, by Schwartz, Perryand Berch) abundant description are arranged all at document.
The preferred detergent-active compounds of available is the negatively charged ion and the non-ionic compound of soap class and synthetic on-soap.
Anion surfactant is well-known to those skilled in the art.Embodiment comprises alkylbenzene sulfonate, and particularly alkyl chain length is C
8～C
15Linear alkylbenzene sulfonate; Uncle and secondary alkyl sulfate, particularly C
8～C
15The primary alkyl phenylsulfate; Sulfated alkyl ether; Alkene sulfonate; Alkylxylene sulfonate; Dialkyl sulfosuccinates; And fatty sulfonate.Generally be preferably sodium salt.
The available ionic surfactant pack draws together primary, secondary alcohol ethoxyl compound, and the ethoxylation C of 1～20 moles of ethylene oxide is on average arranged on especially every mol of alcohol
8～C
20Fatty Alcohol(C12-C14 and C12-C18) on average has the ethoxylation C of 1～10 moles of ethylene oxide on more particularly every mol of alcohol
10～C
15Uncle and secondary Fatty Alcohol(C12-C14 and C12-C18).The ionic surfactant pack of non-ethoxylatedization is drawn together alkyl poly glucoside, glycerol monoethers, and polyhydroxyamide (the glucose acyl is pressed).
The selection of detergent-active compounds (tensio-active agent) and consumption are relevant with the use intention of detergent composition.For example be used for machine dishwasher, generally be preferably more a spot of low bubble nonionogenic tenside.In fabric cleaning composition, skilled formulator is all known, can select different surfaces promoting agent system to the hand washing product with the product that the laundry of different model is machine-washed.
The tensio-active agent total amount that exists is also relevant with final use intention, and for example, in composition for use in dishwasher, its total amount can be low to moderate as 0.5% (weight), or in the composition of hand washing fabric, may be up to as 60% (weight).In the use in washing machine composition, general suitable amounts is at 5～40% (weights).
The detergent composition that is suitable in automatic washing machine generally contains the non-soap surfactant of negatively charged ion, or the combination of nonionogenic tenside or both arbitrary proportions, chooses wantonly and uses with soap.
Anion surfactant, the higher nonionogenic tenside of soap class and ethoxylation generally can be included in the base-material powder.The lower tensio-active agent of ethoxylation is more suitable for the back and adds.
The detergent composition that contains by modified aluminosilicate of the present invention also is suitable for comprising the bleaching system.The present invention relates generally to and contains the composition that can produce the peroxy bleaching compound of hydrogen peroxide in the aqueous solution, for example inorganic or organic peroxide acid, and such as the such inorganic persalt of alkali metal perborate, percarbonate, superphosphate, persilicate and persulphate.As mentioned above, the present invention more specifically relates to the composition that contains SPC-D.
The bleaching component is batched always.
SPC-D can have one deck to prevent deliquescent protective layer.A kind of SPC-D that comprises the protective layer of sodium metaborate and water glass is disclosed in GB 2 123 044 B (Kao company) patent.
Peroxy bleaching compound is 5～35% (weights) as the suitable consumption of SPC-D, is preferably 10～25% (weights).
Peroxy bleaching compound as SPC-D, can be used in combination with bleach-activating agent (bleaching precursor), the bleaching action when hanging down to strengthen wash temperature.The suitable consumption of bleaching precursor is 1～8% (weight), is preferably 2～5% (weights).
Preferred bleaching precursor is a peroxycarboxylic acid precursors, more particularly peroxyacetic acid precursor and benzoyl hydroperoxide precursor and peroxide carbonic acid precursor.Particularly preferredly be applicable to that bleaching precursor of the present invention is N, N, N ', N '-tetra acetyl ethylene diamine (TAED).
A kind of bleaching stibilizer (heavy metal sequestering agent) also can exist.The bleaching stibilizer that is suitable for comprises four acetic acid quadrols (EDTA) and polyphosphonate such as Dequest (trade mark), EDTMP.
In the detergent composition of the silico-aluminate that contains modification of the present invention, can there be other material, be preferably the carbonate of sodium, to increase its soil removability and to be easy to washing operation as basic metal.The yellow soda ash dosage is 1～60% (weight), is preferably 2～40% (weights).But the composition that contains or do not contain yellow soda ash less is also within the scope of the invention.Yellow soda ash can be contained in the base-material powder or the back batching in, or they are within two kinds.
In the base-material powder, mix a small amount of granular structure agent,, can improve powder flowbility as lipid acid (or fatty acid soaps), sugar, acrylate or acrylate/maleic acid ester polymkeric substance.Preferred powder structural agent is a fatty acid soaps, and dosage is 1～5% (weight).
Other material that can exist in the modification detergent composition of the present invention comprises anti-redeposition agent, for example cellulose polymer compound; Soil release polymer; White dyes; Inorganic salt as sodium sulfate and so on; Suitable foaming control agent or foamed promoter; Proteolysis and lipolytic enzyme; Dyestuff; Coloured speckle; Spices; Foaming regulator and fiber softening compound.
The detergent composition that contains modified aluminosilicate of the present invention can prepare with any usability methods.Detergent powder can by spraying drying compatible to the insensitive compound pulp of heat, and then spraying is gone up or after batch that those are not suitable for the composition handled through slurry, suitably prepared.The composition that contains modified aluminosilicate of the present invention is preferably used the preparation of non-spraying drying (non-tower) Process.The base-material powder is that other composition adds (afterwards batching) subsequently by mixing and prilling process preparation.
The base-material powder can suitably prepare with high-speed mixer/granulator.Technological process with high-speed mixer/granulator is disclosed in such as EP 340013A, EP 367339 A, EP 390 251A and EP 420 317 A patents such as (Unilever companies).
Detailed Description Of The Invention
To further be set forth the present invention by following embodiment.
Embodiment 1
The zeolite P that preparation obtains by embodiment 11 methods among the EP A 565 364.Before the drying, but after washing and being filtered into 36% dried solid, with sodium silicate solution (SiO
2: Na
2The O mol ratio is 2) (43% dried solid) join in the zeolite slurry, makes zeolite P/ water glass weight ratio reach 10: 1 (by butt).The slurry of thorough mixing gained, again VOMM drying machine (obtaining) from VOMM Impianti company with direct-fired air (CO in the air
2About 2.2% (weight) of content) being dried to dried solid reaches 90%.
Embodiment 2
Except that the zeolite P/ water glass weight ratio of final slurry (add water glass after) is 100: 7.5 (by butt), all adopt the prescription identical with embodiment 1.
Embodiment 3
The zeolite P that preparation obtains by embodiment 11 among the EP A 565 364.Before the drying, but after washing and being filtered into 35% dried solid, with sodium silicate solution (SiO
2: Na
2The O mol ratio is 2) (43% dried solid) join in the zeolite slurry, makes zeolite P/ water glass weight ratio reach 10: 1 (by butt).Filter this slurry, obtain 40.9% dried solid (d.s.).
(Narlex MA 340, commercially available civilian starch 40%d.s.) mix, and reaching water glass/polymer weight ratio is 20: 2: 1 with the filter cake of gained and polymers soln again.
Subsequently, the material of dry this gained reaches 90%d.s. in laboratory thermopnore moisture eliminator (make Retsch).
Embodiment 4
The zeolite P that preparation obtains by embodiment 11 among the EP-A-565 364.Before the drying, but after washing and being filtered into 35% dried solid, with sodium silicate solution (SiO
2: Na
2The O mol ratio is 2) (43% dried solid) join in the zeolite slurry, makes zeolite P/ water glass weight ratio reach 100: 8 (by butt).Filter this slurry, reach 39.8%d.s..
(Narlex MA 340, commercially available civilian starch 40%d.s.) mix, and reaching water glass/polymer weight ratio is 100: 8: 4 with the filter cake that obtains and polymers soln again.
Subsequently, the material of dry this gained reaches 90%d.s. in laboratory thermopnore moisture eliminator (make Retsch).
The product of embodiment 1～4 gained has following characteristic.
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| d 50μm | 3.12 | 2.8 | 2.8 | 2.8 |
| pH | 11.3 | 11.1 | 11.7 | 11.7 |
| CEBC | 134 | 142 | 137 | 131 |
| Carrier fluid amount % | 83 | 82 | 72 | 73 |
| Sand content % | 0.27 | 0.13 | 0.01 | 0.01 |
Claims (21)
1, Powdered modified aluminosilicate comprises the alkalimetal silicate on the silico-aluminate that is deposited on P type zeolite granular.
2,,, comprise the silico-aluminate of P type zeolite of 65～90% weight and the alkalimetal silicate of 1～20% weight by butt according to the modified aluminosilicate of claim 1.
3,,, comprise the silico-aluminate of P type zeolite of 70～87% weight and the alkalimetal silicate of 1～20% weight by butt according to the modified aluminosilicate of claim 1 or 2.
4,,, comprise the silico-aluminate and 1～20% of the P type zeolite of 75～85% weight, the alkalimetal silicate of weight by butt according to one modified aluminosilicate in aforementioned any claim.
5, according to any one the modified aluminosilicate in the claim 2,3 or 4,, comprise the alkalimetal silicate of 3～15% weight by butt.
6, according to any one the modified aluminosilicate in the claim 2,3 or 4,, comprise the alkalimetal silicate of 5～10% weight by butt.
7, according to the modified aluminosilicate of claim 1, the weight ratio of this P type zeolite aluminosilicate and alkalimetal silicate wherein, by butt, the scope at 100: 20～100: 1.
8, according to the modified aluminosilicate of claim 7, the weight ratio of this P type zeolite aluminosilicate and alkalimetal silicate wherein, by butt, the scope at 100: 15～100: 3.
9, according to the modified aluminosilicate of claim 7 or 8, the weight ratio of this P type zeolite aluminosilicate and alkalimetal silicate wherein, by butt, the scope at 100: 10～100: 5.
10, according to aforementioned each the modified aluminosilicate of claim, wherein alkalimetal silicate is SiO
2With Na
2The mol ratio of O is 1.6～4 water glass.
11, according to aforementioned each the modified aluminosilicate of claim, its weight in average granularity is 1～10 μ m.
12, according to the modified aluminosilicate of right 11, its weight in average granularity is 1.5～6 μ m.
13, according to the modified aluminosilicate of claim 11 or 12, its weight in average granularity is 2.5～5 μ m.
14, according to aforementioned each the modified aluminosilicate of claim, by butt, its CEBC is 110～160 milligrams of CaO/ gram modified aluminosilicates.
15, according to the modified aluminosilicate of right 14, by butt, its CEBC is 130～155 milligrams of CaO/ gram modified aluminosilicates.
16,, also comprise the additive that is selected from phosphonate, aminocarboxylate, multi-carboxylate, Citrate trianion and composition thereof of significant quantity according to aforementioned each the modified aluminosilicate of claim.
17, according to any one the modified aluminosilicate in the claim 1～9, its pH value is between 10～12.
18, according to the production method of the modified aluminosilicate of claim 1,, add a kind of alkalimetal silicate comprising in containing 20～46% solid P type zeolite aluminosilicate slurries, and with gained mixture drying.
19, the method in the claim 18, wherein said slurry contains 30～40% solids.
20, claim 18 or 19 method are wherein introduced carbonic acid gas in drying process.
21, according to the production method of the modified aluminosilicate of claim 1,, in this slurry, add a kind of alkalimetal silicate comprising the slurry of a kind of undried P type zeolite of preparation, and with gained mixture drying.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9605533.0A GB9605533D0 (en) | 1996-03-15 | 1996-03-15 | Modified aluminosilicate |
| GB9605533.0 | 1996-03-15 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1213396A CN1213396A (en) | 1999-04-07 |
| CN1137976C true CN1137976C (en) | 2004-02-11 |
Family
ID=10790490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB971930600A Expired - Fee Related CN1137976C (en) | 1996-03-15 | 1997-03-07 | Modified aluminosilicate |
Country Status (18)
| Country | Link |
|---|---|
| US (1) | US6448218B2 (en) |
| EP (1) | EP0892843B1 (en) |
| JP (1) | JP4110541B2 (en) |
| KR (1) | KR100464891B1 (en) |
| CN (1) | CN1137976C (en) |
| AT (1) | ATE332957T1 (en) |
| AU (1) | AU725258B2 (en) |
| BR (1) | BR9708055A (en) |
| CA (1) | CA2247222A1 (en) |
| CZ (1) | CZ294911B6 (en) |
| DE (1) | DE69736323T2 (en) |
| ES (1) | ES2268726T3 (en) |
| GB (1) | GB9605533D0 (en) |
| HU (1) | HU223053B1 (en) |
| NO (1) | NO984226L (en) |
| PL (1) | PL186173B1 (en) |
| WO (1) | WO1997034980A1 (en) |
| YU (1) | YU38198A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1373494B1 (en) * | 2001-03-29 | 2006-03-01 | Topo Target A/S | Succinimide and maleimide derivatives and their use as topoisomerase ii catalytic inhibitors |
| CN1295312C (en) * | 2005-09-26 | 2007-01-17 | 江南大学 | Method for synthesizing washing adjuvant using concave-convex rod day |
| CN104649291B (en) * | 2014-11-21 | 2017-01-18 | 中国铝业股份有限公司 | Zeolite preparation method |
| DE102015014816B4 (en) * | 2015-11-14 | 2018-01-18 | Audi Ag | Coupling element for connecting fluid-carrying lines and corresponding coupling arrangement |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3740347A (en) * | 1971-06-24 | 1973-06-19 | Grace W R & Co | Acid stable molecular sieve products |
| US4265777A (en) * | 1980-04-17 | 1981-05-05 | The Procter & Gamble Company | Detergent compositions containing an aluminosilicate detergency builder and an unsaturated fatty acid soap |
| JPS5738317A (en) * | 1980-08-12 | 1982-03-03 | Toyo Soda Mfg Co Ltd | Zeolite powder with high fluidity and its manufacture |
| EP0087035B1 (en) * | 1982-02-08 | 1985-09-11 | Union Carbide Corporation | Zeolite-containing detergent compositions and process for preparing same |
| GB9119958D0 (en) | 1991-09-18 | 1991-10-30 | Unilever Plc | Detergent compositions |
| DE4309656A1 (en) | 1993-03-25 | 1994-09-29 | Henkel Kgaa | Process for the production of very finely divided zeolitic alkali metal aluminum silicates |
| DE69408161T2 (en) * | 1993-11-24 | 1998-05-07 | Unilever Nv | DETERGENT COMPOSITIONS |
| ES2134830T3 (en) | 1993-12-10 | 1999-10-16 | Procter & Gamble | STABILIZATION OF INGREDIENTS SENSITIVE TO OXIDATION IN DETERGENT COMPOSITIONS OF PERCARBONATE. |
| GB2287949A (en) * | 1994-03-31 | 1995-10-04 | Procter & Gamble | Laundry detergent composition |
| GB2287948B (en) * | 1994-03-31 | 1998-04-08 | Procter & Gamble | Detergent composition |
| GB9605534D0 (en) * | 1996-03-15 | 1996-05-15 | Unilever Plc | Detergent compositions |
-
1996
- 1996-03-15 GB GBGB9605533.0A patent/GB9605533D0/en active Pending
-
1997
- 1997-03-07 CA CA002247222A patent/CA2247222A1/en not_active Abandoned
- 1997-03-07 PL PL97328970A patent/PL186173B1/en not_active IP Right Cessation
- 1997-03-07 EP EP97908207A patent/EP0892843B1/en not_active Expired - Lifetime
- 1997-03-07 YU YU38198A patent/YU38198A/en unknown
- 1997-03-07 CZ CZ19982938A patent/CZ294911B6/en not_active IP Right Cessation
- 1997-03-07 JP JP53310897A patent/JP4110541B2/en not_active Expired - Fee Related
- 1997-03-07 KR KR10-1998-0707274A patent/KR100464891B1/en not_active IP Right Cessation
- 1997-03-07 AT AT97908207T patent/ATE332957T1/en not_active IP Right Cessation
- 1997-03-07 HU HU9902096A patent/HU223053B1/en not_active IP Right Cessation
- 1997-03-07 BR BR9708055A patent/BR9708055A/en not_active Application Discontinuation
- 1997-03-07 ES ES97908207T patent/ES2268726T3/en not_active Expired - Lifetime
- 1997-03-07 CN CNB971930600A patent/CN1137976C/en not_active Expired - Fee Related
- 1997-03-07 DE DE69736323T patent/DE69736323T2/en not_active Expired - Fee Related
- 1997-03-07 US US09/142,652 patent/US6448218B2/en not_active Expired - Fee Related
- 1997-03-07 WO PCT/EP1997/001208 patent/WO1997034980A1/en active IP Right Grant
- 1997-03-07 AU AU20260/97A patent/AU725258B2/en not_active Ceased
-
1998
- 1998-09-14 NO NO984226A patent/NO984226L/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| DE69736323D1 (en) | 2006-08-24 |
| EP0892843B1 (en) | 2006-07-12 |
| KR20000064597A (en) | 2000-11-06 |
| PL186173B1 (en) | 2003-11-28 |
| NO984226D0 (en) | 1998-09-14 |
| JP4110541B2 (en) | 2008-07-02 |
| HUP9902096A2 (en) | 1999-10-28 |
| AU725258B2 (en) | 2000-10-12 |
| CZ294911B6 (en) | 2005-04-13 |
| PL328970A1 (en) | 1999-03-01 |
| WO1997034980A1 (en) | 1997-09-25 |
| HU223053B1 (en) | 2004-03-01 |
| AU2026097A (en) | 1997-10-10 |
| CN1213396A (en) | 1999-04-07 |
| HUP9902096A3 (en) | 2001-11-28 |
| US20010009895A1 (en) | 2001-07-26 |
| DE69736323T2 (en) | 2007-08-30 |
| KR100464891B1 (en) | 2005-02-28 |
| YU38198A (en) | 1999-09-27 |
| US6448218B2 (en) | 2002-09-10 |
| JP2000506922A (en) | 2000-06-06 |
| NO984226L (en) | 1998-09-15 |
| BR9708055A (en) | 1999-07-27 |
| CA2247222A1 (en) | 1997-09-25 |
| ATE332957T1 (en) | 2006-08-15 |
| EP0892843A1 (en) | 1999-01-27 |
| CZ293898A3 (en) | 1999-05-12 |
| GB9605533D0 (en) | 1996-05-15 |
| ES2268726T3 (en) | 2007-03-16 |
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